The absorption and emission spectra, as well as the photolysis mechanism of p-phenylbenzoyl methanthiol in methanol and in gas phase were elucidated in detail based on the molecular structures of the ground states, ex...The absorption and emission spectra, as well as the photolysis mechanism of p-phenylbenzoyl methanthiol in methanol and in gas phase were elucidated in detail based on the molecular structures of the ground states, excited states and their spectroscopic characters. The TD-M062 X calculations demonstrate that the S_1 state in gas phase will decompose into SH and p-phenylbenzoyl radical via a barrierless process, but the T_1 and T_2 do not photolyze. By adding 1 and 2 methanol molecules onto p-phenylbenzoyl methanthiol, the CPCM model can perfectly describe the solvation effects of methanol. Methanol may stabilize the excitation states, but also protects the resulting radical products from recombination.展开更多
The reaction mechanisms of Ti（~3F） ＋ CH2C12→CH2=TiCl2 and Ti（~3F） ＋ CHC13→HC÷TiCl3 were investigated with Gaussian 03 program package at the B3PW91/6-311＋＋G（d,p）level.The computational results reveale...The reaction mechanisms of Ti（~3F） ＋ CH2C12→CH2=TiCl2 and Ti（~3F） ＋ CHC13→HC÷TiCl3 were investigated with Gaussian 03 program package at the B3PW91/6-311＋＋G（d,p）level.The computational results revealed that：1） Both reaction systems are initiated by Ti（~3F） atom attacking the C atom of CH2C12 and CHCl3 to activate a C-Cl bond;2） Both reaction systems were carried out via triplet reaction channels;3） CH2=TiCl2 has singlet and triplet isomers,and the singlet one is more stable;4） The HOMO of CH2=TiCl2（S） illustrates a π-bonding interaction between C and Ti;5） Only singlet HC÷TiCl3 was located,and the Mulliken atomic spin densities show that the two single electrons are mostly on the C atom.展开更多
The C-C bond activation and recyclization of benzocyclobutenone to poly-fused rings catalyzed by the[Rh(R,S-L)]+complex producing the R,S-,S,R-,R,R-and S,S-product were investigated systematically at the BP86/6-31G(d,...The C-C bond activation and recyclization of benzocyclobutenone to poly-fused rings catalyzed by the[Rh(R,S-L)]+complex producing the R,S-,S,R-,R,R-and S,S-product were investigated systematically at the BP86/6-31G(d,p)level in gas phase and THF,and the R,S-and S,R-reaction pathways were revisited at the M062X/6-31G(d,p)level in THF.The computational results reveal that THF only marginally alters the free-energy barriers,but elevates the relative energies of all species.The BP86 functional testifies that in both gas phase and THF,the activation of strained C-C bonds bears relatively low free-energy barriers,and the rate-determining steps of S,R-and R,R-channels are different from those of R,S-and S,S-channels.The BP86 functional also predicts that the R,S-channel is energetically most favorable in gas phase,but the S,R-product is dominant in THF.The change of NPA charges can mirror the variation of molecular structures to elucidate reaction mechanisms.展开更多
基金jointly supported by the National Natural Science Foundation of China(Nos.21502136 and 51702228)the Natural Science Foundation of Shandong Province(ZR2017LB010)the Scientific Research Initial Foundation for Introduction of Talent of Taishan University(Y-01-2013010)
文摘The absorption and emission spectra, as well as the photolysis mechanism of p-phenylbenzoyl methanthiol in methanol and in gas phase were elucidated in detail based on the molecular structures of the ground states, excited states and their spectroscopic characters. The TD-M062 X calculations demonstrate that the S_1 state in gas phase will decompose into SH and p-phenylbenzoyl radical via a barrierless process, but the T_1 and T_2 do not photolyze. By adding 1 and 2 methanol molecules onto p-phenylbenzoyl methanthiol, the CPCM model can perfectly describe the solvation effects of methanol. Methanol may stabilize the excitation states, but also protects the resulting radical products from recombination.
基金financially supported by the National Natural Science Foundation of China(11174215)Natural Science Foundation of Shandong Province(ZR2012BL10)the University Science and Technology Project of Shandong Province(No.J13LD05)
文摘The reaction mechanisms of Ti（~3F） ＋ CH2C12→CH2=TiCl2 and Ti（~3F） ＋ CHC13→HC÷TiCl3 were investigated with Gaussian 03 program package at the B3PW91/6-311＋＋G（d,p）level.The computational results revealed that：1） Both reaction systems are initiated by Ti（~3F） atom attacking the C atom of CH2C12 and CHCl3 to activate a C-Cl bond;2） Both reaction systems were carried out via triplet reaction channels;3） CH2=TiCl2 has singlet and triplet isomers,and the singlet one is more stable;4） The HOMO of CH2=TiCl2（S） illustrates a π-bonding interaction between C and Ti;5） Only singlet HC÷TiCl3 was located,and the Mulliken atomic spin densities show that the two single electrons are mostly on the C atom.
基金supported by the National Natural Science Foundation of China(No.21571137)the Natural Science Foundation of Shandong Province(ZR2017LB010)the Science and Technology Planning Project(Guidance Plan)of Tai’an City(Nos.2018GX0041 and 2018GX0073)。
文摘The C-C bond activation and recyclization of benzocyclobutenone to poly-fused rings catalyzed by the[Rh(R,S-L)]+complex producing the R,S-,S,R-,R,R-and S,S-product were investigated systematically at the BP86/6-31G(d,p)level in gas phase and THF,and the R,S-and S,R-reaction pathways were revisited at the M062X/6-31G(d,p)level in THF.The computational results reveal that THF only marginally alters the free-energy barriers,but elevates the relative energies of all species.The BP86 functional testifies that in both gas phase and THF,the activation of strained C-C bonds bears relatively low free-energy barriers,and the rate-determining steps of S,R-and R,R-channels are different from those of R,S-and S,S-channels.The BP86 functional also predicts that the R,S-channel is energetically most favorable in gas phase,but the S,R-product is dominant in THF.The change of NPA charges can mirror the variation of molecular structures to elucidate reaction mechanisms.
